Alkylation process and catalyst therefor



United States atent ALKYLATION PROCESS AND CATALYST THEREFOR Herbert R. Appell, Riverside, Ill., assignor to Universal Oil Products Company, Des Plaines, 111., a corporation of Delaware No Drawing. Application November 24, 1954 Serial No. 471,081

24 Claims. '(Cl. 260-448) This invention relates to a novel process for effecting carbonium ion reactions and more particularly relates to the use of the reaction product of a metal halide of the Friedel-Crafts type and a halogenated'fatty acid as 'a catalyst for promoting reactions involving a carbonium ion. The invention is specifically concerned with the use of new types of catalysts for increasing the rates of reaction between an alkylatable compound and an olefinacting compound.

An object of this invention is to provide "a novel catalyst for promoting carbonium ion reactions.

Another object of this invention is to produce an alkylated organic compound and particularly an alkylated isoparaflinic hydrocarbon.

A further object of this invention is to react an alkylatable compound and an olefin-acting compound in the presence of a novel catalyst.

One embodiment of this invention relates to a catalyst having the general formula MX,,(OOCR),,, wherein M is a metal capable of forming a metal halide of the Friedel-Crafts type, X a helogen, n an integer less than 4, R a halogenated alkyl group, and an integer less than 4 such that n plus y equals the valence of the metal M.

Another embodiment of this invention relates to a catalyst prepared by reacting at least equimolecular proportions of a halogenated fatty acid with a metal halide of the Friedel-Crafts type.

A further embodiment of this invention relates to a process characterized by the formation of a carbonium ion which comprises contacting a compound capable of forming a carbonium ion with a carbonium ion acceptor at reaction conditions with a catalyst comprising the reaction product of a metal halide of the Friedel-Crafts type and a halogenated 'fatty acid, said final catalyst substantially free of said metal halide.

A specific embodiment of this invention relates to a process which comprises reacting an alkylatable compound and an olefin-acting compound at alkylating conditions in the presence of a catalyst comprising the reaction product of a metal halide of the Friedel-Crafts type and a halogenated fatty acid, said catalyst substantially free of said metal halide.

A further specific embodiment of this invention relates to a polymerization process which comprises contacting polymerizable material at polymerizing conditions with a catalyst comprising the reaction product of a metal halide of the Friedel-Crafts type and a halogenated fatty acid, said final catalyst substantially free of said metal halide.

In another specific embodiment this invention relates to an isomerization process which comprises contacting isomerizable material at isomerizing conditions in the presence of a catalyst comprising the reaction product of a metal halide of the Friedel-Crafts type and a halogenated fatty acid, said final catalyst substantially free of said metal halide.

A still further specific embodiment of this invention relates to a catalyst comprising the reaction product of 2. aluminum chloride and trifluoroacetic acid, said catalyst substantially free of aluminum chloride.

Carbonium ion reactions are hydrogen transfer and alkyl transfer effected through the mechanics of forming a positive ion of a nature of RCH wherein R represents a hydrocarbon residue. Some typical examples of carbonium ion reactions include the synthesis of specific compounds such as esters by reacting alkyl halide, for example, with an organic acid; polymerization of propylene and/or butylene to recover useful normally liquid material; production of mixtures having specific characteristics as, for example, the alkylation of isobutane or isopentane or both with propylene to form highly branched chain molecules boiling in the gasoline range and other reactions involving hydrogen or alkyl transfer as an essential result of the reaction.

In a specific aspect, however, the invention is particularly directed to alkylation reactions as specified hereinbefore in the embodiments of this invention.

Alkylatable compounds which may be used as starting materials in this process comprise hydrocarbons, hydroxy hydrocarbons, and the like. The hydrocarbons include both branched chain alkanes and cyclic hydrocarbons, the preferred cyclic hydrocarbons being those of the aromatic series. The aromatic hydrocarbons including benzene hydrocarbons such as benzene, toluene, the Xylenes, ethylbenzene and other 'alkylbenzenes containing at least 1 replaceable nuclear hydrogen atom. Polycyclic aromatic hydrocarbons such as naphthalene, alkyl naphthalenes and other polynuclear hydrocarbons which contain at least 1 replaceable nuclear hydrogen atom are also alkylated by olefin-acting compounds as herein set forth. The hydroxy hydrocarbons include particularly the phenols, naphthols and other hydroxy aromatic hydrocarbons, including monohydroxy and polyhydroxy aromatic hydrocarbons, an example of the latter being hydroquinone. The aromatic hydrocarbons including the benzene hydrocarbons may be obtained from any source such as by the distillation of coal, by the dehydrogenation of naphthalenic hydrocarbons, by the cyclization of aliphatic hydrocarbons and by other means. The cyclic hydrocarbons also include alkylatable cycloparafiins such as alkylcycloentane and alkylcyclohexane hydrocarbons. Branched chain paraffins such as isobutane, isopentane and other branched chain alkanes may also be charged to the alkylation treatment as herein set forth.

Suitable alkylating agents which may be charged in this process are olefin-acting compounds including monoolefins, diolefins, polyolefins, also alcohols, ethers, esters, the latter including alkyl halides, alkyl phosphates, certain alkyl sulfates and also esters of various organic carboxylic acids. The preferred alkylating agents are olefinic hydrocarbons which comprise monoolefins having one double bond per molecule and polyolefins which have more than one double bond per molecule. Monoolefins which may be utilized for alkylating aromatic hydrocarbons and other alkylatable compounds in the presence of the catalyst of this invention are either normally gaseous or normally liquid and includes ethylene, propylene, butylenes, pentenes and highly normally liquid olefins, the latter including various polymers of gaseous olefins, particularly polymers having from 6 to 18 carbon atoms per molecule. Cycloolefins such as cyclopentene, cyclohexene, and various alkylcycloolefins may also be used. Other unsaturated hydrocarbons used as alkylating agents in this process include conjugated diolefins such as butadiene and isoprene, non-conjugated diolefins, other polyolefin hydrocarbons containing more than two double bonds per molecule, terpenic hydrocarbons, etc.

When employed in a polymerization process, the catalyst of this invention promotes polymerization reactions by contacting polymerizable material at a temperature of from about C. to about 200 C. and at super-atmospheric pressure. The exact operating conditions depend upon the nature of the charge stock used since some charge stocks, for example isobutylene, are easier to polymerize than others, for example propylene. It will be advantageous to use high pressure in effecting this reaction since the equilibrium towards the product would be aided by the mass action principle and since the normally gaseous reactants may be maintained in the liquid phase. The pressure employed is generally super-atmospheric but moderate; in the range of from about 50 to about 500 psi.

As hereinbefore mentioned, the catalyst may also be utilized in isomerization reactions. Isomerization reactions are generally effected at temperatures of from about 50 C. to about 400 C. and the pressure may vary from subatmospheric to super-atmospheric. The carbonium ion producing catalyst in the case of isomerization effects a rearrangement of the molecular. structure to produce isomers of the original material without, substantially changing the molecular weight. Isomerization reactions are use ful in increasing the octane rating of straight run gasoline which is usually composed of hydrocarbon molecules having a long straight chain or slightly branched chain structure by changing the molecular structure to be more branched. Isomerization is also a useful reaction for producing a particular material. For example, para-xylene may be produced by fractionating or otherwise separating the para-xylene from an equilibrium mixture of paraxylene and the other xylene isomers and then isomerizing the separated xylene mixture in the presence of the catalyst of this invention to form an equilibrium mixture of para-xylene and the other isomers. This process may be repeated on the newly formed equilibrium mixture again and again until virtually all of the material originally present has been converted to para-xylene.

The catalyst of this invention is the reaction product of a metal halide of the Friedel-Crafts type and a halogenated fatty acid. Metal halides of the Friedel-Crafts type include those catalysts utilized in the classical Friedel-Crafts reaction. The halides of aluminum, zinc, iron, zirconium, tin, beryllium, tantalum, and boron are generally suitable for the purposes of the invention and are the more important metal halides of the Friedel- Crafts type. The metal is represented by the symbol M in the present specification and claims. The halogen is represented by the symbol X and the metal halide may be represented by the formula MX wherein n+y repre sents the valence of the metal. For example, if M is aluminum n+y is equal to 3 since the halogens are monovalent. The letters n+y have also previously been defined in the embodiment of the invention. Aluminum chloride is a preferred metal halide since it is readily available and since the results when using aluminum chloride show that this chloride generally eifects the desired reaction in a preferred manner. It is to be understood, however, that other metal halides of the Friedel- Crafts type may be used although not necessarily with the equivalent results.

Preferred catalysts comprise the reaction product of aluminum chloride with trifiuoroacetic acid, aluminum chloride with trichloroacetic acid, aluminum chloride with difiuoroacetic acid, aluminum chloride with dichloroacetic acid, aluminum chloride with monofluoroacctic acid, and aluminum chloride with monochloroacetic acid.

Aluminum chloride and aluminum bromide are well known Friedel-Crafts catalysts and are known for their activity in promoting a Wide variety of organic chemical reactions. These aluminum halide catalysts, however, because of their pronounced activity in promoting condensation reactions between certain organic reactions, often form sludge complexes with the reactants, especially reactants which contain a relatively reactive group, or onewhich is-readily removed from a hydrocarbon molecule in'the presence of an aluminum halide and at the reaction conditions utilized.

In many instances inwhich the aluminum halide catalyst is utilized, extensive side reactions may occur or the reactants may polymerize or condense to such an extent that high molecular weight tarry materials are produced. Because of these undesirable characteristics of the aluminum halide catalysts, the processes in which they are employed are generally characterized by relatively high catalyst losses and relatively low efiiciencies. In contrast to these aluminum halides the use of the catalyst of my invention is characterized by low catalyst losses and high efiiciencies. When using the catalyst of my invention these tarry materials or acid sludges, as they are called, are greatly reduced and often are not formed. Since free Friedel-Crafts type metal halide is not an essential of the catalyst of this invention, and since it is the free halide which causes the acid sludge or tarry material, the catalyst of the present invention is preferably free of free Friedel-Crafts type metal halide; that is there are no substantial quantities or concentrations of halide as such as in the catalyst of my invention and, as hereinbefore mentioned, this is an essential feature of the present invention.

The catalyst of the present invention may be in the form of a solid, liquid, in solution'in a suitable solvent or impregnated into a solid absorbent material. The catalyst may be used by itself or in mixture with other suitable carbonium ion producing substances; however, as hereinbefore mentioned, the catalyst is preferably not used in admixture with free Friedel-Crafts metal halides.

When a solid absorbent carrying material is utilized, the catalyst may be impregnated into the absorbent material by using a solution of the catalyst in a suitable solvent followed by. drying of the composite. The catalyst may also be directly placed on the absorbent material by contacting the absorbent material with the molten catalyst.

The absorbent carrying materials which may be used will vary somewhat. in their absorptive capacity, and also in their chemical and physical properties and their influence upon the catalytic efiect of the mixtures. The materials. which may be employed are divisible roughly into three classes. One class comprises materials of a predominantly siliceous character and includes diatomaceous earth, kieselguhr and artificially prepared porous silica such as, for example, Sil-O-Cel. In the case of naturally occurring diatoms it is believed that they sometimes contain minor amounts of' highly active. aluminum oxide which in some instances seems to contribute to the total catalytic effect of the solid catalyst. This active material is not present in the artificially prepared forms of silica.

Another class of materials which may be employed either alone: orv in conjunction with the first class comprises, generally, certain members of the class of aluminum silicates and includes such naturally occurring substances as the various fullers earth and clays as bentonite, montmorillonite, etc. The class also includes certain artificially prepared aluminum silicates of which the product known as tonsil is representative, this substance being in a sense a purified aluminum silicate made by treating certain selected clays with sulfuric, hydrochloric or other mineral acid and washing out the reaction products. The naturally occurring substances in this general class are characterized by a high adsorptive capacity which is particularly in evidence in making up the present type catalyst, and they may also contain traces of active ingredients which may assist in producing desired efiects. Again each silicate material which may be used alternatively will exert its own specific influence upon the net eifectiveness of the catalyst composite which will not necessarily be identical with that of the other members of the class.

The third class of absorptive materials comprises forms of porous carbonaceous material or porous forms of carbon. Materials in this class appear to possess particular ability to hold the catalyst so that the catalyst often has -.exceptionally'high activity. The porous forms of carbon evidently prevent the breakdown of the Catalyst. Specifically preferred materials are charcoal, coke, etc. These charcoals or coke may be used in the regular form or they may be activated forms.

The catalyst of the present invention may be prepared by mixing a metal halide of the Friedel-Crafts type and a halogenated fatty acid at conditions to effect reaction between the two, and in the reaction at least one hydrogen halide molecule is formed. I

The term halogenated fatty acids is intended to include those acids in which the carboxyl group is attached to a halogenated parafiin residue. Specifically included acids are halogenated acetic acid, halogenated propionic acid, halogenated butyric acid, halogenated valeric acid, halogenated caproic acid, halogenated caprylic acid, etc. Of these acids, halogenated acetic acid and halogenated propionic acid are more preferred since these acids have proven to be better acids to use to prepare the catalyst of this invention. The invention, however, is directed to halogenated fatty acids. The fatty acids may be completely or partially halogenated; for example, the acetic acid used may be a monohaloacetic acid, a dihaloacetic, or a trihaloacetic fatty acid. The trihaloacetic acids, especially trifluoroacetic acid and trichloroacetic acid are preferred. Likewise, when the halogenated fatty acid is propionic acid, the molecule may contain one, two, three, four, or five halogen atoms. When a polyhalogenated fatty acid is employed the halogen atoms in the molecule may be different. The halogenated fatty acid may be represented by the formula HOOCR, wherein HOOCR is the carboxyl acid radical and R represents a holagenated alkyl group.

The halogen in the halogenated fatty acid is preferably fluorine and/ or chlorine with a bromine and iodine being less preferred.

The catalyst employed in this process is prepared conveniently by mixing the powdered metal halide of the Friedel-Crafts type with the halogenated fatty acid. The compounds react with the liberation of hydrogen chloride. The amounts of the individual compounds are controlled so that at least one of the halogens in the metal halide of the Friedel-Crafts type remains in the final compound. For example, when reacting aluminum chloride with tn'fiuoroacetic acid, a mol to mol ratio may be maintained and the final catalyst may be represented by the formula A1CI (OOCCF In this type of reaction one molecule of hydrogen chloride is liberated from one molecule of aluminum chloride. As another example, reacting two mols of trifluoroacetic acid with one mol of aluminum chloride, a compound having the formula AlCl(-OOCCF is produced. In this reaction two molecules of hydrogen chloride are produced from one molecule of aluminum chloride. As hereinbefore mentioned, it is preferred that the third chlorine atom in the aluminum chloride molecule remains asso ciated with the aluminum, that is, it is preferred that the third chlorine is not replaced by a trifluoroacetate radical.

The reaction between the two compounds may be performed at low or high temperatures. One very satisfactory method of preparing the catalyst is to cool the acid to near its freezing point and to pour the cold acid over the aluminum halide. The resultant compound is usually a free flowing powder that reacts vigorously with water. Since the catalyst is affected by water it is important that the conditions in the reaction zone be maintained substantially dry and further the reactants introduced to the reaction zone should be dried before introduction thereto.

The process of this invention may be carried out in batch operation by placing an alkylatable compound and the catalyst in an autoclave and stirring while an olefin hydrocarbon is added gradually thereto, the reaction mixture being maintained at an elevated temperature at which alkylation of the hydrocarbon takes place. After the re action has occurred, the reactor is then cooled and the alkylation product is recovered from the resultant reaction mixture.

It is preferred, however, to carry out this process in a continuous manner. This may be accomplished by placing a fixed bed of catalyst within a reactor such as a steel tube and the reactants, that is, the alkylatable compound and the olefin-acting compound are then passed continuously through the bed of catalyst at alkylation conditions. The alkylation product is then recovered from the reactor effluent and any unreacted alkylatable compound and olefin-acting compound may then be recycled to the reaction zone. Fluidized type of operation may also be employed in the presence of the aforementioned catalyst. In this method of operation, a charging stock is passed upwardly through a bed of finely divided catalyst causing the catalyst particles to become set in motion'and form a fluid-like mass. Inasmuch as the alkylation reaction is exothermic, a portion of the catalyst may be withdrawn from the reaction zone either intermittently or continuously, the withdrawn catalyst is cooled and then returned to the reaction zone in order to provide a convenient method of temperature control. Another mode of operation which may be employed is the moving bed type of operation wherein a compact bed of the catalyst is passed continuously through the reaction zone either concurrently or countercurrently to the incoming reactants, the catalyst is then passed into a cooling zone from which it is returned to the reaction zone. Another alternative type of operation comprises suspending finely divided solid catalyst in a stream of charging stock and treating said suspension under suitable conditions of temperature and pressure to produce the desired alkylation reaction.

The temperature at which the alkylation process of this invention may be conducted is dependent upon the charging stocks being employed. However, the alkylation process is generally carried out at a temperature of from about 0 C. to about 300 C. and preferably at a temperature of from about 10 C. to about C. Pressure aids the reaction of alkylation and consequently this process is preferably effected at a super-atmospheric pressure which is generally not in excess of about 200 atmospheres.

In carrying out the alkylation of aromatic compounds, and particularly of aromatic hydrocarbons, an olefinacting compound, an olefin-containing hydrocarbon fraction, or other olefin-acting compound may be commingled with a reacting aromatic compound so that the ratio of alkylatable compound to olefin-acting compound in a total mixture charged to the alkylation zone is approximately 5:1 on a molar basis. In some cases this molar ratio of alkylatable compound to olefin may be as low as about 1:1 or as high as 10:1 or even 50:1, the exact ratio being dependent somewhat on the particularly alkylatable compound and olefinic hydrocarbon or other olefin-acting material charged to the process.

Alkylated compounds formed in this process may be used as intermediates for organic synthesis or utilized for other purposes. Thus alkylated aromatic hydrocarbons which are formed from benzene and olefins or fiom other aromatic hydrocarbons and olefins are useful as starting materials in the production of detergents, insecticides, synthetic rubber, etc. Also certain alkylated hydrocarbons are valuable as motor fuel constituents because of their relatively high octane numbers.

The following examples are given to illustrate this invention but they are introduced With no intention of limiting unduly the generally broad scope of the invention.

EXAMPLE I A catalyst was prepared by the reaction of 11.4 grams of tr fluoroacetic acid upon 13.3 grams of resublimed aluminum chloride powder. The trifluoroacetic acid was pro-cooled to near its freezing point by placing it in some powdered Dry Ice before use. The cold acid was poured over the aluminum chloride with repeated stirring. The resulting compound AlCl (--OOCCF was a free flowing powder that was not wet readily by water. This catalyst is designated catalyst A.

EXAMPLE II A catalyst was prepared by the reaction of 11.4 grams of trifiuoroacetic acid upon 6.65 grams of resublimed aluminum chloride powder. The catalyst was prepared as described in Example I. The catalyst had the formula AlCl(-OOCCF This catalyst is designated catalyst B.

EXAMPLE III A catalyst was prepared by the reaction of 11.4 grams of trifiuoroacetic acid upon 4.4 grams of resublimed aluminum chloride powder. The catalyst was prepared as described in Example I. This catalyst had the formula AI(OOCCF This catalyst is designated catalyst C.

EXAMPLE IV A fourth catalyst was prepared similar to that outlined in Example I; however excess aluminum chloride was used and therefore the final catalyst contained free aluminum chloride. This catalyst is designated catalyst D.

EXAMPLE V Each of the above described catalysts was separately tested to determine their individual effectiveness as alkylation catalysts. 10 grams of each of the catalysts was placed in a turbomixer equipped with a 1000 ml. stainless steel pot. The charge stock comprised the following mixture:

0.2% C l-I The charge stock was pumped into the reactor or turbomixer. The amount used for each run was approximately the same and the exact amounts are shown in the table below. The operating conditions and results are also shown in the following table.

Table Catalyst A B C D Starting Temperature C 24. 5 28. 5 29. 20. Maximum Temperature C 31.0 35. 0 34. 0 37. 0 Pressure, p.s.i 410 405 415 410 223 223 223 223 66. 7 42. 7 20. 0 Liquid Product, Percent Yield Based on Olefins Charged 215. 2 157. 6 69. 7

Considerab1e acid sludge was formed using this catalyst containing free aluminum chloride and, therefore, the total liquid received was not representatire of the alkylate produced.

The above examples illustrate that the catalysts as set forth in the specification and examples are eifective 'alkylation catalysts.

EXAMPLE VI 8 EXAMPLE v11 10 grams of the catalyst as used in Example VI is charged to a rotating autoclave with grams of a mixture of equal parts of propylene and propane. The autoclave is sealed and the contents heated to a temperature of 116 C. and maintained at this temperature for a period of two hours. After the two hour period the auto clave is opened, the contents discharged, and the hydrocarbon phase separated from the catalyst phase. An analysis of the mixture shows that a substantial portion of the propylene is converted to higher boiling normally liquid material.

I claim as my invention:

1. A catalyst having the general formula wherein M is a metal of a Friedel-Crafts type metal halide, X a halogen, n an integer less than 4, R a halogenated alkyl group, and y an integer less than 4 such that n plus y equals the valence of the metal, said catalyst being substantially free of uncornbined metal halide.

2. A catalyst having the general formula where X is a halogen, n an integer less than 3, and R a halogenated alkyl group, said catalyst being substantially free of uncombined aluminum halide.

3. A catalyst having the general formula AlCl (OOCR) wherein R is a halogenated alkyl group, said catalyst be ing substantially free of uncornbined aluminum chloride.

4. A catalyst having the general formula wherein R is a halogenated alkyl group, said catalyst being substantially free of uncornbined aluminum chloride. 5. A catalyst having the formula AlCl (-OOCCF said catalyst being substantially free of uncornbined aluminum chloride.

6. A catalyst having the general formula AlCl (OOCCF 2 said catalyst being substantially free of uncornbined aluminum chloride.

7. A catalyst prepared by metathetically reacting at least equimolecular proportions of a halogenated fatty acid with a metal halide of the Friedel-Crafts type to produce said catalyst under conditions whereby hydrogen halide is eliminated.

8. A catalyst prepared by metathetically reacting at least two molecular proportions of a halogenated fatty acid with a metal halide of the Friedel-Crafts type to produce said catalyst under conditions whereby hydrogen halide is eliminated.

9. A catalyst prepared by metathetically reacting at least equirnolecular proportions of trihaloacetic acid with aluminum chloride to produce said catalyst under conditions whereby hydrogen chloride is eliminated.

10. A catalyst prepared by metathetically reacting at least equimolecular proportions of trichloroacetic acid with aluminum chloride to produce said catalyst under conditions whereby hydrogen chloride is eliminated.

11. A catalyst prepared by metathetically reacting at least equimolecular proportions of trifluoroacetic acid with aluminum chloride to produce said catalyst under conditions whereby hydrogen chloride is eliminated.

12. A process characterized by the formation of a carboniurn ion which comprises contacting a compound capable of forming a carbonium ion with a carbonium ion acceptor at reaction conditions with a catalyst having the general formula MX (OOCR) wherein M is a metal of a Friedel-Crafts type metal halide, X a halogen, n an integer less than 4, R a halogenated alkyl group, and y an integer less than 4 such that 11 plus y equals the aesaase 9 valence of the metal, said catalyst being substantially free of uncombined metal halide.

13. A polymerization process which comprises contacting polymerizable material at polymerizing conditions with a catalyst having the general formula MX,,(OOCR) where M is a metal of a Friedel-Crafts type metal halide, X a halogen, it an integer less than 4, R a halogenated alkyl group, and y an integer less than 4 such that n plus y equals the valence of the metal, said catalyst being substantially free of uncombined metal halide.

14. An isomerization process which comprises contacting isomerizable material at isomerizing conditions in the presence of a catalyst having the general formula MX,,(-OOCR) wherein M is a metal of a Friedel- Crafts type metal halide, X a halogen, 11 an integer less than 4, R a halogenated alkyl group, and y an integer less than 4 such that n plus y equals the valence of the metal, said catalyst being substantially free of uncombined metal halide.

15. A process which comprises reacting an alkylatable compound and an olefin-acting compound at alkylating conditions in the presence of a catalyst having the general formula MX,,(-OOCR),,, wherein M is a metal of a Friedel-Crafts type metal halide, X a halogen, n an integer less than 4, R a halogenated alkyl group, and y an integer less than 4 such that n plus y equals the valence of the metal, said catalyst being substantially free of uncombined metal halide.

16. A process which comprises reacting an alkylatable hydrocarbon and an olefin-acting hydrocarbon at alkylating conditions in the presence of a catalyst having the general formula AlX,,(--OCR) wherein X is a halogen, In an integer less than 3, and R a halogenated alkyl group, said catalyst being substantially free of uncombined aluminum halide.

17. A process which comprises reacting an alkylatable hydrocarbon and an olefin-acting hydrocarbon at alkylating conditions in the presence of a catalyst having the gen- 10 eral formula A1Cl (-OOCR) wherein R is a halogenated alkyl group, said catalyst being substantially free of uncombined aluminum chloride.

18. A process which comprises reacting an alkylatable hydrocarbon and an olefin-acting hydrocarbon at alkylating conditions in the presence of a catalyst having the general formula AlCl(-0OCR) wherein R is a halogenated alkyl group, said catalyst being substantially free of uncombined aluminum chloride.

19. A process which comprises reacting an isoparafiin and an olefin at alkylating conditions in the presence of a catalyst having the general formula AlCl (OOCCF said catalyst being substantially free of uncombined aluminum chloride.

20. A process which comprises reacting an isoparafim and an olefin at alkylating conditions in the presence of a catalyst having the general formula AlCl(OOCCF said catalyst being substantially free of uncombined aluminum chloride.

21. The catalyst of claim 1 further characterized in that R is 3.

22. The catalyst of claim 2 further characterized in that R is -cF,.

23. The catalyst of claim 1 further characterized in that R is --CCl 24. The catalyst of claim 2 further characterized in that R is -CCl References Cited in the file of this patent UNITED STATES PATENTS 2,142,980 Huijser et al. Jan. 3, 1939 2,182,617 Michel Dec. 5, 1939 2,376,508 Sachanen et al May 22, 1945 2,379,656 Ruthrufi July 3, 1945 2,446,897 Young et a1 Aug. 10, 1948 2,468,746 Greensfelder et al May 3, 1949 2,475,358 Moore et al. July 5, 1949 

1. A CATALYST HAVING THE GENERAL FORMULA
 16. A PROCESS WHICH COMPRISES REACTING AN ALKYLATABLE HYDROCARBON AND AN OLEFIN-ACTING HYDROCARBON AT ALKYLATING CONDITIONS IN THE PRESENCE OF A CATALYST HAVING THE GENERAL FORMULA AIXN(-OOCR)3-N, WHEREIN X IS A HALOGEN, N AN INTEGER LESS THAN 3, AND R A HALOGENATED ALKYL GROUP, SAID CATALYST BEING SUBSTANTIALLY FREE OF UNCOMBINED ALUMINUM HALIDE. 